Stabilized rosin size



Patented Aug. 1 2, 1952 STABILIZED ROSIN SIZE Charles C. Price, South Bend, Ind, assignor to. Hercules Powder Company, wilmingtomDel a corporation of Delaware No Drawing. ApplicationOctober 25,

" Serial No. 782,227

13 Claims. (01. 105 218 This invention relates in general to a stabilized. material and in particular to a natural resin stabilized with an aryl nitro compound.

Rosin and rosinlike materials are generally characterized by beingrelatively susceptible to 5 oxidation under the normal conditions of storage and use. For example, a rosin-containing film}. powder or emulsion is characterized by rapid" Y deterioration upon exposure to the atmosphere and for this reason it is highly desirable to devise 10 a method for inhibiting the oxidation of rosin materials.

Now in accordanee with the present invention,

a natural resin or a modified natural resin is stabilized against deterioration by the incorporation therein of an aryl nitro compound and optionally a paraflin oiL Thus, in the preparation of a resin composition, a material containing at least one nitro group on an aromatic nucleus is incorporated into the resin, whereby the deterioration by oxidation is substantially inhibited. The aryl nitro compound may conveniently be added to the resin at a stage inits preparation or compounding such as, for example, to the refined resin prior to its formation into a soap, emulsion or the like, or alternatively after the preparation of the resin-containing material.

The general nature of the invention having" been described, the following examples are presented in illustration of specific methods for carrying out the invention.

EXAMPLE 1 One hundred parts of a partially decarboxylated gum rosin was heated to 90-100 C. and 0.5 part m-dinitrobenzene was added thereto. The rosin was then dispersed in water according to conventional techniques using about 5 parts of casein, about 7 parts of 28% ammonia and 0 suificient water to produce a 40% solids dispersion. The resulting material was a fine rosin dispersion stabilized against oxidation.

To 100 parts of a partially decarboxylated gum rosin heated to 90-100" C. there were added 0.5 part m-dinitrobenzene and -5' parts paraffin oil.

A dispersion of this resin in water was prepared by the procedure-of Example 1.

. EXAMPLE .3

To 100 parts of a partially decarboxylated gum rosin heated to -100"C. there were, added 0.5 part trinitrotoluene and 5 parts paraifinfoil,

dispersion of this resin in water was prepared by the procedure of Example 1.

EXAMPLE 4 To parts of a partially decarboxylated rosin heated to '90-100". C; there were addedf0g5 part1,3,5-trinitrobenzene and 5 partsparafiin oil. 'A dispersion of this resin in water Was'pre rosin heated to 910-100" C. there-"were added 1.0

part m-dinitrobenzene and 5 parts parafiin oil. A dispersion of this resin in water was prepared by the procedure of Example 1. V

EXAMPLE 6 To 100 parts of'a partially decarboxylatedguin; rosin heated to 90-100 C. there was addedLO- part m-dinitrobenzene. resin in water was Example 1.

'A' dispersion of this EXAMPLE '7 To 100 parts of a partially decarboxylated gum rosin heated to 90-100 C. there were added 1 part m-dinitrobenzene and 2 parts parafiin oil.

A dispersion of this rosin in water was prepared according to the procedure oi Example 1.

EXAMPLE 8 T0100 partsof a partially decarboxylated gum rosin heated to 90-100 C. there was added -3 parts m-dinitrobenbene. A dispersion of this rosin in water was prepared according to the procedure of Example 1.

EXAMPLE 9 The procedure of the previous examples. was

EXAMPLE 10- The procedure of the preceding examples was repeated using 1% Z-nitro-lA-diaminobenzene.

EXAMPLE 11 The procedure of the preceding examples was repeated using, 1% 2,iedinitrodiphenylamine.

. JliiXAMPLE lZ j One hundred partsof K gum rosin was heated to 100 C. and 05 part m-dinitrobenzene and'5, parts parafiin oil were added thereto. The rosin was'dispersed in water according to the pro! e u e Exam j prepared by" the procedure of 3 The effectiveness of the aryl nitro compounds used according to Examples 1-12 was determined by comparing the oxidation resistance of the product to a similar composition containing no the sample maintained at 70 C. for 4 hours. The sample had absorbed oxygen corresponding to a pressure difierential of only 2 mm. of mercury, While the sample under identical conditions added antioxidant. Four different methods were 5 containing no oxidation inhibitor absorbed oxyused to measure the beneficial efiects of the gen corresponding to a pressure differential of antioxidant. According to the first method, a film 35 mm. of the resin material was cast on a glass plate EXAMPLE 14 and allowed to stand in air at room tempera" A 40 alcohol solution of a rosin meth lester ture for 3 weeks. The effectiveness of the oxicontairgng 05% m dimtmbenzene as a stgbmzer dation inhibitor was measured by the length of was tested as in Example The rosin methyl i for whlch P filmhremameg i g ester containing m-dinitrobenzene absorbed oxybnttle- Aecordmg to t e sewn me es gen corresponding to a pressure differential of 11 paper cards were cemented t9gether.wlth the mm. of mercury, while a similar sample containtm of am a wlth simflarfoxn' 15 ing no inhibitor absorbed oxygen corresponding positions containing no antioxidants and allowed to a pressure difieremial of 38 mm of mercury to stand in air at room temperature. The effectiveness of the oxidation inhibitor was measured PLE 5 by the lengfl} of tlme for f setlsfeetery bend A 40% alcohol solution of partially decarboxylmg was retalned- Aeeordmg to the e method ated gum rosin containing 0.5% m-dinitrobenzene of testing, a two-gram sample of the dlspersien was tested according to the procedure of Exto be tested Was pleced in a Volumemc amples 1s and 14. The rosin containing m-diflask and Covered Wlth grams of send- The nitrobenzene absorbed oxygen corresponding to fl w W evacuated at 70 P remove an the a pressure differential of 9 mm. of mercury while water and was then flooded with o y at this rosin with no inhibitor absorbed oxygen mospheric pressure and the system closed. The corresponding to a pressure difi ti l 07297 amount of oxidation was measured by the drop mm in pressure as determined by a mercury manom- EXAMPLE 16 eter. According to the fourth method of testing, a weighed sample of the water dispersion A slze was prepared from centnfuged was spread over a large amount of sand, all the gum msm by sapomficatlon ueder heat and P water removed under vacuum and the dried samsure and spray drymg eccordmg to eenvennone'l ple'on the sand was stored under oxygen at 300 procedures To a portlon of the he prepared p. s. i. in an oxygen bomb at room temperature 7 g g tg fi added 05% m'd}n}trobenzene for 7 days. The sample was again dried under w 1 e dry SIZE and m'dmltrobenzene vacuum and weighed were dissolved in acetone. The solvent was re- The test data for Examples 1-12 according to moved leavmg stabmzeddry size" themethods of testing are presented in Table 1. EXAMPLE 17 v In each case, the resin composition containing The above procedure was repeated using 1% the aryl n tro compound showed increased oxida- 40 mdinitmbenzene as the stabilizer tion resistance according to each of the tests applied, the oxidation resistance generally being EXAMPLE 13 measurably increased by the copresence of To 100 parts of centrifuged K gum rosin were parafiln oil. added 0.5 part m-dinitrobenzene and 6 parts Table 1 Percent Tackiness of lgaqgmgmc Oxygen Type of Resin Percent Aryl Nitro Compound Paraffin Film on Glass gfi (pres sg e d ill r fi t Oil Plate y ference mm. Gain in Hg) Weight Example 1. Partially decarlaoxyl- 0.5%m-dim'trobenzene None.. About3wks.. About6-8wks...

- ated gum rosm. 7 Example 2. .do...; do Example 3. 0.5% trinitrotoluene Example 4. 0.5% 1, 3, 5-trinitrobenzene. Example 5. l 0% m-dinitrobenzene 5" Example 6. do Example 7. .d0 Example 3 3% m-dinitrobenzene Example 9. 1% nitrated phenyl-B-naphthylamine. Example 10. 1% Z-nitro-l, i-diaminoben- None.... do 27 Z911 ExamplelL l%2,i-dinitrodiphenylamine. None. ..do 251 Control for -None None.... Less thanl day. Less than3days 499 9,5

itxfimples Exam leiz. Kgum rosin... 0.5% m-dinitrobenzene 5% 49 Controlfor do None None 330 Example EXAMPLE 13 paraflin oil. A dry size was prepared from the There was prepared a 40% alcohol solution of FF wood rosin containing 0.5% m-dinitrobenzone. A sample of this containing 2 grams of rosin was placed on 30 grams of sand according to the manometric oxidation procedure described for the previous eramples. The alcohol was rethus treated rosin by saponification and spray drying by the procedure of Example 16.

EXAMPLE 19 Two-gram samples of each of the dry sizes in Examples 16-18 were placed in oxidation flasks moved by evaporation under reduced pressure and and these sample w e j cted to oxidation zit-120910. for. 170 minutes according to the. manometric oxidation technique: described for Examples l-ll'. was noted as indicated: by the data in Table 2 wherein: there' was a measurable decrease inoxygen absorption in the. treated dry sizes as compared with a dry size containing no oxidation.

inhibitor. The test data from Examples 13-15 are included in Table: 2"for comparison.

Significant oxidation resistance matic nuclei.

6 aromatic. nucleus in an aromatic organic compound. In the specific examples, there are shown various aromatic nitro compounds containing one or more nitro groups on relatively simple aro- It will be understood, however, that other and more complicated aromatic radicals may be used. such asrfor example, various:

mono-, diandi polycyclic aromatic compoundsasrf'well as heterocyclic aromatic compounds and Table 2 Rosin. Composition Inhibitor (-Ary1 Nitro) Example. 13. Control for Ex p Example l5 Control for Exam lei-5 Example 16; Example 17.

Example 18... Control for Ex. 16-18;"

FF woodrosiu Partially (lecarboxy-- .lated gumrosin.

K gum rosin dry size fNone 0.5% m-d'initrobenzene 1.0% m-dinitrobenzene I 0.5 %m-dinitrobenzene None;

difference None 2' N'onc.. None".. 11 Nona-.. 38 None"-. 9

Nonc. 297 V Nona... 170 Nonc 118 6% 215 None'.... 430

In selecting the resin for the composition according'to this invention, there may be. used the various grades of wood or gum rosin as desiredsuch as, for example, an FF wood rosi-norone of the paleror darker grades of rosin and natural resins.- Thus, there may be used rosin itself, hydrogenated rosin, polymerized rosin, partially decarboxylated rosin, heat-treated rosin, or the like, as well asrosin esters, rosin amine, and

been obtained by using as the rosin a mixture of 4 two ormore resins and other natural resinssuch as, for example, a mixture of an ordinary wood or gum rosin together with a partially or substantially gasoline-insoluble dark-colored rosin lay-product material.

Thus, the term natural resin as used in the specification; and claims will be'understoodtoinclude materials such as wood or gum rosin and also rosinlike materials and modified rosins and resins which are similar in properties to. rosin and are characterized by being saponifiable to form. materials substantially like rosinates; and the term resinate, therefore, includesthe substantially neutral, saponified material obtained therefrom.

Various rosin modifiers such as plasticizers and. other rosin compatible nonrosin materials and. compositions may beadded tothecomposition it'-, self or to the resin prior to its compoundingto.

an extent conforming with its, compatibility with the resin, in order to improve or. modify the physical or chemical properties oiithe resin component or the dry resinate composition. For .example, small amounts of plasticizers and rosin extenders may be included in the composition to improve theproperties thereof or to reduce the cost of the composition. I I

The arylnitro compound used as. the stabilizing agentaccording to this invention isicharacterized by having at least one nitro group directly on an the like. Likewise, it will be understood that the.

aromatic nucleus may have other groups substituted thereon such as, for example, alkyl, aryl, halogen, amino, and the like, aswell as oxygencontaining groups such as, for example, alkoxy, carboxyl, and the like. Thus, for example, there may be used the various mono-, diand the polynitro-substituted aromatic compounds as will be readily apparent to those skilled in. the ark.

Typical nitro-containing compounds which. have been found satisfactory are. m-dinitrobenzene, 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene, 2,4-dinitroto1uene, nitrobenzene, nitrated phenyl B naphthylamine, 2 nitro 1,4 diaminobenzene, 2,4-dinitrodiphenylamine, and the like. In addition tothese specifically named nitro compounds, it will be understood, of course, that there may be used other aromatic compounds characterized by having at least one nitro group substituted on an aromatic nucleus.

Instead. of the parafiin oil specifically disclosed. in the examples, there may be used as, the coacting stabilizing agent other oils, waxes and waxlike. materials such as vegetable or mineral.

oils and waxes. including, in addition to. paraifin oil, paraffin wax, petrolatum, crude scale wax,

certain napthenic-base petroleum oils,. various,

waxes, and the like.

The stabilizing agents may be incorporated nto the. resin at any desired or convenient stage in the preparation of the refined resin material of the resin-containing composition. For example, when it is desired to prepare a stabilizedv of. resin.' Similarly, where it is desired to prepare a resin emulsion, it will be convenient to add .the stabilizing agents as above or, preferably, to add the stabilizing agents during the preparation of the emulsion. Likewise, in the 79 preparation of a dry resin compositionisuch as,

for example, a dry, saponified resin, the stabilizing agents may be. added prior to, during, or

afterthe saponification or drying of the composition. For example, the stabilizing agents may be added during the saponification of the 7.. resin prior to the drying step in which case it has generally been found advisable to avoid excessive or drastic conditions during the subsequent operations in order to prevent loss of the stabilizing agents through chemical action or volatilization. Alternatively, the agents may be added to the dried composition, and in the case of a'dry, saponified rosin material it has generally been found quite satisfactory to treat the dry material with a solution of the stabilizing agents preferably in a solvent which is a nonsolvent for the saponified rosin.

The proportions of the stabilizing agents may be varied within relatively wide; limits. For example, an amount of the aryl nitro compound as low as about 0.1% adds a substantial degree of stability to the resin composition. This stabilizing agent may be used in. amounts up to.

as high as 5% based on the amount of rosin above which amount the stability is increased only to a minor extent. The preferred range of proportion is about A to about 3% ofthe nitro compound. Similarly, the amount of the paraflin oil may be varied fromabout 1 to about 10% and preferably in the neighborhood of about 5%, although substantial stability is imparted by the nitro compound in the absence of What I'claim and'desire to protect by Letters Patent is:

' l A stabilized rosin size resistant to oxidation comprising, inparticulate form, a member selected from the group consisting of rosin, saponified rosin, and mixtures thereof and containing a stabilizing amount of an aryl nitro compound said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the groupconsisting of amino, phenyl and methyl, the nucleus of said aryl compound being derived from the group consisting of benzene and naphthalene.

2. A stabilized paste rosin size, resistant to oxidation, comprising an aqueous emulsion of rosin and. a stabilizing amount of an aryl nitro compound said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl and methyl, the nucleus of said aryl compound being derived from the group consisting of benzene and naphthalene.

3. A stabilized paste rosin size, vresistant to oxidation, comprising an aqueous emulsion of rosin and a stabilizing amount of parafiin wax an aryl nitro compound said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl and methyl, the nucleus of said aryl compound being derived from the group consisting of benzene and naphthalene.

4. A stabilized paste rosin size, resistant to oxidation, comprising an aqueous emulsion of rosin and a stabilizing amount of an aryl nitro compound, said aryl nitro compound having.

from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl, and methyl, the nucleus of said compound being derived from benzene.

5. A stabilized paste rosin size, resistant to oxidation, comprising an aqueous emulsion of rosin and a stabilizing amount of paraffin oil and an aryl nitro compound, said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl, and methyl, the nucleus of sai d compound being derived from benzene.

6. A stable paste rosin size, resistant to oxidation, comprising a high free rosin aqueous" emulsion of rosin and saponified rosin together with between about 1 and about 10% of a paraffin oil and between about 0.1 and about 5% of 8. A stable paste rosin size, resistant to oxida comprising a high free rosin aqueous tion, emulsion of rosin and saponified rosintogether with about 5% paraffin oil and between about 0.5 and about 3% of 1,3,5-trinitrobenzene.

9. A stable paste rosin size, resistant to oxidation, comprising a high free rosin aqueous emulsion of rosin and saponified rosin together with about 5% parafiinoil and between about 0.5 and about 3% of 2,4,6-trinitrotoluene.

10. A stable dry rosin size resistant to oxidation comprising in particulate form saponified rosin and a stabilizing amount of an aryl nitro compound said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl and methyl, the nucleus of said aryl compound being derived from the group consisting of benzene and naphthalene.

11. A stable dry rosin size resistant to oxidation comprising in particulate form saponified rosin and a stabilizing-amount of a paraffin oil and an aryl nitro compound said aryl nitro compound'having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl and methyl, the nucleus of said aryl compound being derived from the group consisting of benzene and naphthalene.

12. A stable dry rosin size resistant to oxidation comprising in particulate form' saponified rosin and about 5% parafiin oil and between about 0.5 and about 3% of an aryl nitro compound, said aryl nitro compound having from 1 to 3 nitro groups attached to the aryl nucleus and which may contain as additional substituents only members selected from the group consisting of amino, phenyl, and methyl, the nu- 9 10 cleus of said compound being derived from ben- UNITED STATES PATENTS zene' Number Name Bat 13. A stable dry rosin size resistant to oxida- 1379.235 witty May 241921 tion comprising in particulate form saponified 1,946,322 Kennedy 6 1934 rosin and about 5% paraflin oil and between 5 1,988,300 Clark Jan 15, 1935 about 0.5% and about 3% of dinitrobenzene. 2,244,075 Mikeska June 3' 1941 CHARLES PRICE- 2,294,724 Dreshfield Sept. 1, 1942 REFERENCES CITED 2,384,061 Auer Sept. 4, 19 45 The following references are of record in the 1 file of this patent: 

1. A STABILIZED ROSIN SIZE RESISTANT TO OXIDATION COMPRISING, IN PARTICULATE FORM, A MEMBER SELECTED FROM THE GROUP CONSISTING OF ROSIN, SAPONIFIED ROSIN, AND MIXTURES THEREOF AND CONTAINING A STABILIZING AMOUNT OF ARYL NITRO COMPOUND SAID ARYL NITRO COMPOUND HAVING FROM 1 TO 3 NITRO GROUPS ATTACHED TO THE ARYL NUCLEUS AND WHICH MAY OBTAIN AS ADDITIONAL SUBSTITUENTS ONLY MEMBERS SELECTED FROM THE GROUP CONSISTING OF AMINO, PHENYL AND METHYL, THE NUCLEUS OF SAID ARYL COMPOUND BEING DERIVED FROM THE GROUP CONSISTING OF BENZENE AND NAPHTHALENE. 